J. M. Carnerero

Covalent and Non‐Covalent DNA–Gold‐Nanoparticle Interactions: New Avenues of Research

The interactions of DNA, whether long, hundred base pair chains or short-chained oligonucleotides, with ligands play a key role in the field of structural biology. Its biological activity not only depends on the thermodynamic properties of DNA-ligand complexes, but can and often is conditioned by the formation kinetics of those complexes. On the other hand, gold nanoparticles have long been known to present excellent biocompatibility with biomolecules and are themselves remarkable for their structural, electronic, magnetic, optical and catalytic properties, radically different from those of their counterpart bulk materials, and which make them an important asset in multiple applications. Therefore, thermodynamic and kinetic studies of the interactions of DNA with nanoparticles acting as small ligands are key for a better understanding of those interactions to allow for their control and modulation and for the opening of new venues of research in nanomedicine, analytic and biologic fields. The interactions of gold nanoparticles with both DNA polymers and their smaller subunits; special focus is placed on those interactions taking place with nonfunctionalized gold nanoparticles are reviewed in the present work.

Spectroscopic study of the ground and excited state prototropic equilibria of 4-azaindole.

The ground and singlet excited state prototropism of 4-azaindole, 4AI, in acid and basic aqueous solutions, inside and outside the pH range, has been systematically studied by using absorption and fluorescence spectroscopic techniques. These studies have thrown light on some interesting aspects on the nature and the photophysics of the 4-AI prototropic species. Thus, the changes of the 4AI absorption spectra reveal the existence of four ground state species; the pyridinic protonated cation, C (pK(a)(C)=7.5±0.1), the neutral molecule, N (pK(a)(N)=15.5±0.5), the pyrrolic deprotonated anion, A, and a previously unnoticed dication, DC (pK(a)(DC)=-4.6±0.4). Besides the emissions of these species, a new fluorescence profile appears in alkaline solutions at around 500nm. This extra band has been ascribed to the neutral phototautomer, NT. What is more relevant to this study is the fact that the position and the intensity of the emission band assigned to the monoprotonated cation are very different from those observed for the normal cation of the 7-azaindole, 7-AI. This together with the fact that for the formation of the DC species a cationic precursor with a quinoid structure must be invoked, have prompted us to assign this cationic emission to the isomeric CI cations. Finally, the excited-state pK(a)s of the prototropic species of 4AI have been theoretically estimated by using the Förster-Weller cycle.

Exploring Factors for the Design of Nanoparticles as Drug Delivery Vectors

To achieve optimal results when employing nanoparticles in biomedical fields, choosing the right type of nanoparticle and determining the correct procedure for drug loading are key factors. Each type of nanoparticle presents a determined set of characteristics that are, in some cases, unique. In general, their surface charge, geometry or hydrophilic character may be limiting factors, depending on what their intended application is. Once synthesized, additional factors, such as their interaction with biological systems and liberation mechanisms into the target cells, also need to be taken into account. Multiple advantages arise from the use of nanoparticles, such as the capability to solubilize hydrophobic compounds and an increased bioavailability. Those advantages justify the extensive and delicate study that should be undertaken in order to use them as drug delivery agents. One of the most important factors for the design of a drug delivery system with nanoparticles is achieving a high drug-to-nanoparticle ratio. In this Minireview, all of these key factors, both physicochemical and biological, are described, and special emphasis is placed on loading methods employed to introduce drugs into nanoparticles.

A colorimetric study of the interaction of cationic and anionic surfactants with anionic gold nanoparticles

The interactions of citrate-capped 10-nm gold nanoparticles with a cationic model surfactant, CTACl, and an anionic one, SDS, are explored. Results show that for CTACl, values of the c.m.c. close to those reported in the absence of nanoparticles can be obtained by simple colorimetric measurements. For SDS, its interaction with the same-charge nanoparticles is explored through the use of an indirect colorimetric method involving NaCl addition, and a surfactant-nanoparticle interaction model is postulated in this basis. C.m.c. measurements for SDS in the presence of AuNPs show that, despite both substrates being anionic, SDS micelle formation is actually promoted in the presence of gold nanoparticles.